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Related Experiment Videos

Five-coordinate Pd(II) orthometallated triarylphosphite complexes.

Robin B Bedford1, Michael Betham, Craig P Butts

  • 1School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK. r.bedford@bristol.ac.uk

Dalton Transactions (Cambridge, England : 2003)
|January 11, 2007
PubMed
Summary

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Orthopalladated triarylphosphite complexes react with phosphines to form five-coordinate palladium(II) species. These labile complexes readily convert to four-coordinate species, showcasing dynamic coordination chemistry.

Area of Science:

  • Organometallic Chemistry
  • Coordination Chemistry
  • Palladium Catalysis

Background:

  • Orthopalladated triarylphosphite complexes are key intermediates in palladium chemistry.
  • Understanding the coordination behavior of palladium(II) with multidentate phosphine ligands is crucial for catalytic applications.
  • The lability and reactivity of five-coordinate palladium complexes influence reaction pathways.

Purpose of the Study:

  • To investigate the reaction of orthopalladated triarylphosphite complexes with specific phosphine ligands.
  • To characterize the resulting four- and five-coordinate palladium species.
  • To explore the solution-phase lability and reactivity of the synthesized five-coordinate complexes.

Main Methods:

  • Synthesis and characterization of orthopalladated triarylphosphite complexes.

Related Experiment Videos

  • Reaction of palladium complexes with bis(2-diphenylphosphinoethyl)phenylphosphine and 1,1,1-tris(diphenylphosphinomethyl)ethane.
  • X-ray crystallography for structural determination of key complexes.
  • Reactivity studies with hydrogen peroxide and gold(I) chloride.

    • Main Results:

    • Formation of five-coordinate palladium(II) species with bis(2-diphenylphosphinoethyl)phenylphosphine, with crystal structure elucidated.
    • Demonstration of lability in solution, with five-coordinate complexes reacting to form four-coordinate species.
    • Solid-state formation of four-coordinate complexes with 1,1,1-tris(diphenylphosphinomethyl)ethane, while solution studies suggest potential five-coordinate species.

    Conclusions:

    • Five-coordinate palladium(II) complexes derived from orthopalladated triarylphosphites are labile in solution.
    • The coordination number and geometry of palladium complexes are sensitive to the phosphine ligand and reaction conditions.
    • These findings provide insights into the dynamic nature of palladium coordination chemistry relevant to catalysis.